WO2004086151A1

WO2004086151A1 - Holographic recording medium and recording method therefor

Info

Publication number: WO2004086151A1
Application number: PCT/JP2004/003684
Authority: WO
Inventors: Toshihisa Takeyama
Original assignee: Konica Minolta Medical & Graphic, Inc.
Priority date: 2003-03-24
Filing date: 2004-03-18
Publication date: 2004-10-07
Also published as: US20040197670A1; JP2004287138A; EP1610191A4; EP1610191A1

Abstract

A holographic recording medium is characterized in that a holographic recording layer is interposed between a first base material and a second base material; that the holographic recording layer comprises a binder compound (A) having a reactive group, a polymerizable compound (B) having an ethylene double bond in the molecule, a photopolymerization initiator (C), and a crosslinking agent (D) having a functional group reactive with the reactive group of the binder compound (A); and that the photopolymerization initiator (C) contains at least a compound represented by the following general formula (1): (1) (wherein Dye+ represents a cationic dye, R1-R4 respectively represent a substituted or unsubstituted alkyl, aryl, aralkyl, alkenyl, alkynyl, heterocyclic ring, or cyano group, and two or more of R1-R4 may combine together to form a ring.)

Description

Description Holographic recording media and its recording method

The present invention relates to a holographic recording medium capable of increasing the capacity, and more particularly to a holographic recording composition and a holographic recording method suitable for the medium. Background art

In recent years, the exchange of high-speed, large-capacity data has increased due to the spread of the Internet and the adoption of broadband, and the expansion of e-government promoted by governments of various countries has led to a rapid increase in the amount of data stored at each institution. Have been. Furthermore, it is expected that high-capacity recording media will be required in the future due to the spread of high-definition television and the spread of terrestrial digital broadcasting, and the next generation of optical recording media such as Blu-ray discs will become popular in the future. It seems to do. However, with regard to the next generation of recording media, although various methods have been proposed, they are still absent.

Among the next-generation recording media, page-type memory systems, especially holographic recording, have been proposed as an alternative to conventional memory devices, and have recently attracted attention because of their high storage capacity and random access. Are gathering. The holographic recording is described in detail in several reviews (for example, see Non-Patent Document 1). As a recording method in the holographic recording, for example, a recording method using a holographic recording medium in which a transparent base material is disposed on both sides of a holographic recording layer (for example, see Patent Document 1), a holographic recording layer There has been proposed a recording method using a holographic recording medium provided with a reflection surface disposed on one side of the recording medium (for example, see Patent Document 2). In this recording medium, the holographic recording layer, which determines the performance, can be said to be a key technology.

Such a holographic recording layer basically records information by changing the refractive index in the layer by holographic exposure, and reproduces information by reading the change in the refractive index in the recorded medium. Based on the principle, the Holodafic recording layer is made of a material using an inorganic material (for example, see Patent Document 3), a material using a compound that is structurally isomerized by light (for example, see Patent Document 4), or Various materials have been proposed, such as a material utilizing diffusion polymerization of a photopolymer (for example, see Patent Document 5). Among these, in the case of a material using a photopolymer described in Patent Document 5, a volatile solvent is used when preparing a recording layer forming composition, so that the thickness of the material is at most 150. m. In addition, the volume shrinkage of 4 to 10% caused by the polymerization adversely affected the reliability of reproducing the recorded information.

In order to improve the above-mentioned drawbacks, there have been proposed holographic recording layer forming compositions utilizing cationic polymerization with no solvent and relatively small volume shrinkage (for example, see Patent Document 6). However, since the recording layer forming composition is a liquid substance other than the monomer that causes photo-induced thione polymerization, island-shaped portions formed by photopolymerization of the monomer in the recording layer due to holographic exposure move. There is a drawback that the volume of liquid material expands due to changes in the environmental temperature inside the device. Was. Therefore, radical polymerization is used for recording in holographic exposure, and a composition in which a binder matrix is formed after the formation of a medium to retain the radical-polymerizable monomer before the exposure (for example, see Patent Document 7) Has been proposed. By using this composition, the thickness of the holographic recording layer can be increased, and furthermore, the volume shrinkage is small and the reliability of information obtained at the time of reproduction can be increased.

On the other hand, when performing holographic recording on a holographic recording medium, it is essential to be able to expose with low energy in order to improve the recording speed. In order to improve the recording speed, in other words, the recording sensitivity, the selection and combination of the radically polymerizable monomer, the binder matrix, the photosensitive dye and the radical initiator used are important. For example, a combination of a specific sensitizing dye and a radioactive ray generating agent (for example, see Patent Document 8) has been proposed, but it cannot be said that it is still sufficient.

ίPatent Document 1]

U.S. Pat. No. 5,719,691

[Patent Document 2]

JP 2002-123949 A

[Patent Document 3]

UK Patent 9,929,953

[Patent Document 4]

JP 10-340479 A

[Patent Document 5]

U.S. Pat. No. 4,942,112

[Patent Document 6] U.S. Pat. No. 5,759,721

[Patent Document 7]

U.S. Patent No. 6,48 2,55 1

[Patent Document 8]

JP-A-6-1 30880

[Non-Patent Document 1]

"Holographic D ata S torage (Springer Seriesin Optical Sciences, Vo 1.76)" by Hans J. Coufa 1 et al. (Spr, inger—Verlag GmbH & Co.KG, 2000 08 Month)

The present invention has been made in view of the above problems, and an object of the present invention is to provide a holographic recording medium having high sensitivity and a holographic recording method using the same. Disclosure of the invention

The above object of the present invention has been achieved by the following configurations.

1. A holographic recording layer is sandwiched between a first base material and a second base material, and the holographic recording layer has a reactive group-containing binder compound (A), and an ethylenic double bond in the molecule. A polymerizable compound (B) having the formula (I), a photopolymerization initiator (C), and a crosslinking agent (D) having a functional group capable of reacting with the reactive group of the binder compound (A) having the reactive group. A holographic recording medium comprising at least a compound represented by the following general formula (1) as the photopolymerization initiator (C). General formula (1)

Dye +

1x4--B-f? 2

R ₃

(Wherein, Dy e ⁺ represents a cationic dye, represents FU～R ₄ are each a substituted or unsubstituted alkyl group, Ariru group, Ararukiru group, an alkenyl group, an alkynyl group, a heterocyclic group, or Shiano group, also ! ^ ~ 1 ₄ may form a ring two or more are combined with each other.)

2. At least one is a substituted or unsubstituted alkyl group of the substituents represented by 1 ^ to 1 ₄ of the photopolymerization initiator represented by the general formula (1) (C), Ararukiru group, alkenyl Le group Alternatively, the holographic recording medium according to item 1, which is an alkynyl group and the other substituent is a substituted or unsubstituted aryl group or a heterocyclic group.

3. The cationic dye represented by Dye ⁺ of the photopolymerization initiator (C) represented by the general formula (1) is a methine dye, a polymethine dye, a triarylmethane dye, an indolin dye, or an azine dye. , A thiazine dye, a xanthene dye, an oxazine dye, an ataridin dye, a cyanine dye, a carbocyanine dye, a hemicyanine dye, a rhodocyanine dye, an azamethine dye, a styrinole dye, a pyrilium dye, a thiopyrylium dye or represented by the following general formula (2). 2. The holographic recording medium according to item 1, wherein the holographic recording medium is a coordination metal complex.

General formula (2) M ^{n +} (L) _x

(Where M represents a metal atom, n represents an integer of 1 to 4, L represents a ligand, and X represents an integer of 1 to 6)

4. The hologram according to item 3, wherein L, which is a ligand of the coordination metal complex represented by the general formula (2), is a dye capable of chelating at least two sites on a metal. Traffic recording media.

5. A binder having a reactive group (A) or a crosslinking agent having a functional group capable of reacting with a reactive group of the binder compound (A) having a reactive group (D) Force A siloxane bond or carbon in the molecule 2. The holographic recording medium according to item 1, wherein the holographic recording medium is a compound having a monofluorine bond.

6. The reactive group of the binder compound (A) having a reactive group is a hydroxyl group, a mercapto group, a lipoxyl group, an amino group, an epoxy group, an oxetane group, an isocyanate group, a carbodiimide group, an oxazine group, and a metal alkoxide. 2. The holographic recording medium according to item 1, wherein the holographic recording medium is at least one type of reactive group selected from the group consisting of:

7. The holographic recording medium according to item 5 or 6, wherein the binder compound (A) having a reactive group is liquid at room temperature or has a melting point of 50 ° C. or less.

8. The holographic recording according to item 1, wherein the polymerizable compound (B) having an ethylenic double bond in the molecule contains a compound having a (meth) atalyloyl group in the molecule. media.

9. The polymerizable compound (B) having an ethylenic double bond in the molecule has a refractive index of

I. The holographic recording medium according to item 1, comprising at least 55 or more compounds.

10. When the thickness of the first substrate is d1, the thickness of the second substrate is d2, and the thickness of the holographic recording layer is Dh, 0.15 Dh / (dl + d2 3. The holo-daraphic recording medium according to item 1, characterized by satisfying a relationship of ≤ ≤ 2.0.

I I. Thickness of the holographic recording layer Dh force 200 ^ m or more, 2. Omm Holographic recording medium according to item 10, characterized in that: 12. The holographic recording medium according to item 10, wherein the relationship between the thickness d1 of the first base material and the thickness d2 of the second base material is d1≤d2.

13. The holographic recording according to item 1, wherein the first base material is transparent, and a surface opposite to a surface on which the holographic recording layer is laminated is subjected to an antireflection treatment. Media.

14. The holographic recording medium according to item 1, wherein the material of the first base material is glass.

15. The item described in item 1, wherein a reflective layer having a reflectance of 70% or more is laminated on the surface of the second base material on which the holographic recording layer is laminated or on the opposite surface. Holographic recording media.

16. The holographic recording medium according to item 1, wherein the holographic recording medium has a disk shape.

17. The holographic recording medium according to item 1, wherein the holographic recording medium is force-shaped.

18 · A holographic recording layer is sandwiched between the first base material and the second base material, and the holographic recording layer is formed of a binder compound (A) having a reactive group and an ethylenic compound in the molecule. A polymerizable compound (B) having a double bond, a photopolymerization initiator (C), and a crosslinking agent (D) having a functional group capable of reacting with the reactive group of the binder compound (A) having the reactive group. A method for holographic recording on a holographic recording medium containing at least the compound represented by the general formula (1) as the photopolymerization initiator (C), wherein a binder having a reactive group is provided before holographic exposure. The compound (A) and the crosslinking agent (D) having a functional group are activated by heat or photopolymerization initiator (C). After cross-linking by unirradiated light irradiation, holographic exposure based on the information to be recorded is performed to activate the photopolymerization initiator (C), and this active species has an ethylenic double bond in the molecule. A holographic recording method comprising recording information on a holographic recording medium by diffusing and polymerizing a polymerizable compound (B).

19. After the information recording on the holographic recording medium is completed, the recorded information is stabilized by further irradiating the entire holographic recording medium with heat or light. The holographic recording method described in 1.

20. A holographic recording layer is sandwiched between the first base material and the second base material. The holographic recording layer comprises a binder compound (A) having a reactive group, A polymerizable compound (B) having a heavy bond, a photopolymerization initiator (C) and a crosslinking agent (D) having a functional group capable of reacting with a reactive group of the binder compound (A) having the reactive group. A holographic exposure method based on information to be recorded in a holographic recording method for a holographic recording medium, wherein the holographic recording medium contains at least a compound represented by the general formula (1) as the photopolymerization initiator (C). The photopolymerization initiator (C) is activated, and the active species diffuses and polymerizes the polymerizable compound (B) having an ethylenic double bond in the molecule, whereby information is recorded on the holographic recording medium. Record Holographic recording method characterized in that, after information recording on the holographic recording medium is completed, the entire holographic recording medium is further irradiated with heat or light to stabilize the recorded information. . BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the holographic recording composition of the present invention and the holographic recording medium using the composition as a recording layer will be described in detail.

The holographic recording composition used in the recording layer of the holographic recording medium of the present invention includes a binder compound (A) having a reactive group and a polymerizable compound (B) having an ethylenic double bond in the molecule. ), A photopolymerization initiator (C) and a crosslinking agent (D) having a functional group capable of reacting with the reactive group of the binder compound (A) having the reactive group, and the photopolymerization initiator (C) Is characterized by containing at least a compound represented by the general formula (1).

The complex of a thiothionic dye and boron anion, which are contained at least as a photopolymerization initiator (C), which is an essential component of the holographic recording composition described above, is a complex with a photoradical initiator conventionally used. Compared with an initiator system formed by combining a sensitizing dye for spectrally sensitizing the initiator to the wavelength of an exposure light source for holographic exposure, the boron anion part that generates radicals has a lower sensitizing dye. Radicals can be generated efficiently because they are near the cationic dye, which can be easily adjusted to the light source wavelength used for holographic exposure by changing the structure of the cationic dye. it can.

In addition, in the compound represented by the general formula (1), examples of the boron anion include the following anions. B— 1 B-2 B— 3

B B-8 B-9

B— 10 B-11 B-12

B-13 B-14 B-15

B— 16 B-17 B-18

B— 19 B— 20 B-21

B— 22 B— 23

B-26 B— 27

In order to efficiently generate a radical in the boron anion described above, at least one of the substituents represented by R i to R ₄ in the boron anion portion is a substituted or unsubstituted alkyl. Group, an aralkyl group, an alkenyl group or an alkyl group, and the other substituent is preferably a substituted or unsubstituted aryl group or a heterocyclic group. Such an alkyl group is preferably a linear or branched alkyl group. And a methyl group, an ethyl group, a butyl group, an isobutyl group, a hexyl group, an octynole group, a stearyl group and the like. The alkylene group and the alkynyl group preferably have 2 to 20 carbon atoms. The cycloalkyl group is preferably a 5- to 7-membered ring. Benzinole groups are preferred as the aralkyl group. As the heterocyclic group, a heterocyclic group having aromaticity is preferable, and examples thereof include a thiophene group. The aryl group is preferably a phenyl group or a naphthyl group. These groups may be further substituted. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a hydroxy group, an amino group (including an alkyl-substituted amino group), an alkoxy group, Rubamoyl group, one CO〇R, -OCOR (R is an organic group such as an alkyl group or an aryl group).

Preferred combinations of substituents are one where an alkyl group or a benzyl group, Is preferably an aryl group.

Further, as the cationic dye represented by Dye ⁺ in the compound represented by the general formula (1), a cationic dye conventionally used in various fields can be appropriately selected and used. , Among which methine dye, polymethine dye, triarylmethane dye, indoline dye, azine dye, thiazine dye, xanthene dye, oxazine dye, ataridine dye, cyanine dye, carbocyanine dye, hemishyayun dye, rhodashyun dye, azamethine dye, styryl Dyes, pyrylium dyes, thiopyrylium dyes and coordination metal complexes represented by the following general formula (2) are preferred.

General formula (2) ^{Mn +} (L) _x

Further, the ligand represented by L in the general formula (2) is a dye capable of chelation at two or more sites with respect to a metal ion. From the viewpoint of the stability of the coordination metal complex, It is preferable that the wavelength of the exposure light source for holographic exposure is 500 nm or more because the spectral maximum wavelength can be easily adjusted.

Examples of such a dye capable of chelating at two or more sites include the following dyes.

L-7 one

.-9

(Wherein at least one of the carbon bonds to the azo bond is replaced with a nitrogen, oxygen, sulfur, selenium or tellurium atom, and at least one ring is composed of 57 atoms. X ₂ represents a group of atoms necessary to complete a carbocyclic or heterocyclic ring of the group, and X ₂ represents a group of atoms necessary to complete at least one ring of 57 carbon or heterocyclic rings. The carbocycle or heterocycle may be substituted. G represents a chelating group, W represents one COR ₇ or one CSR ₇ , Y represents one O—, one S—, one N =, one NH— or one NR ₈ —, and Z represents 0 or S And m and n each represent an integer of 1 to 5. 1 and ₁₂ represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkoxy group, an alkylsulfonamide group, an arylsulfonamide group, an anilino group, an acylamino group, an alkylureido group, and an arylureido group. , An alkoxycarbonyl group, an alkoxycarbonylamino group, a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxy group, an aryl group or a heterocyclic group, and R ₇ is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkyl group. A sulfonamide group, an arylsulfonamide group, an aerino group, an acylamino group, an alkylperido group, an arylureido group, a carbamoyl group, a sulfamoyl group, an aryl group or a heterocyclic group, and R ₈ is an alkyl group, an alkenyl group; Group, aryl group or Represents a heterocyclic group. )

The metal ions represented by M ^{n +} in the general formula (2) include silver (I), aluminum (III), gold (III), cerium (III, IV), and cobalt (II, III). , Chromium (III), copper (1, II), europium (III), iron (II, III), gallium (III), germanium (IV), indium (III), lanthanum (III), manganese (II) ), Nickel (II), palladium (II), platinum (II, IV), rhodium (II, III), luteum (II, III, IV), scandium (III), silicon (IV), samarium (III), Titanium (IV), uranium (IV), zinc (II), zirconium (IV), etc., and among these, in the case of a bidentate dye, it can be coordinated in a tetradentate or hexadentate. A metal ion is preferable, and in the case of a tridentate dye, a metal ion capable of coordinating at a hexadentate is preferable. Particularly preferred metal ions are zinc (II), nickel (II), cobalt (III, III), copper (II), rhodium (II, III), ruthenium (11, III), palladium (II), Platinum (II, IV) can be mentioned.

The above-described complex of the cationic dye and boron ion may be used alone.

Two or more kinds may be used in combination. Further, if necessary, in addition to the photopolymerization initiator (C), which is an essential component of the present invention, a conventionally known benzoin and its derivative, a carbonyl compound such as benzophenone, azobisisobutyronitrile, etc. Such as azo compounds, sulfur compounds such as dibenzothiazolyl sulfide, peroxides such as benzoyl peroxide, halides such as 2-tribromomethanesulfonyl pyridine, and oxides such as odonium salts and sulfonium salts. A combination of a compound, a photo-radical initiator such as an iron arene complex and a metal π complex such as a titanocene complex, and a sensitizing dye for spectrally sensitizing the initiator to an exposure light source wavelength for holographic exposure. May be used in combination.

Such a photopolymerization initiator cannot be generally determined by the molecular weight of the photopolymerization initiator (C) or the proportion of the ethylenic double bond in the polymerizable compound having an ethylenic double bond (Β). Although it is not possible, it is usually preferred to use from 0.01 to 25 parts by mass with respect to the polymerizable compound (Β) having an ethylenic double bond.

Next, the binder compound (Α) having a reactive group, which is an essential component of the holographic recording composition, will be described.

When producing the holographic recording medium of the present invention described in detail below, the binder compound is a liquid composition at room temperature or a liquid composition at a temperature of 100 ° C. or lower. It is made by sandwiching it with a predetermined thickness at room temperature, so that a compound that is liquid at room temperature or has a melting point of 100 ° C, It is preferable because deterioration of the initiator (C) due to heat can be prevented.

Furthermore, the recording composition is prevented from flowing in the media after the formation of the media. 4 003684

16

For this purpose, it is preferable to fix a part of the information or fix the information recorded after the holographic recording. As a method of fixing the binder compound, a binder compound having a reactive group (A) and the binder compound The object can be achieved by causing a crosslinking reaction with a crosslinking agent (D) having a functional group capable of reacting with the reactive group of (A). The reactive group contained in the binder compound (A) having a reactive group mentioned herein can be used without particular limitation as long as it reacts with the crosslinking agent (D). Among them, a hydroxyl group, Those having at least one reactive group selected from a mercapto group, a carboxyl group, an amino group, an epoxy group, an oxetane group, an isocyanate group, a carbodiimide group, an oxazine group and a metal alkoxide are preferred. Further, in holographic recording, a binder compound having a reactive group (A) and a binder compound having the reactive group (A) are provided because a refractive index difference between a holographic exposed portion and a non-exposed portion is provided by diffusion polymerization of a monomer. The refractive index of a binder matrix formed from a cross-linking agent (D) having a functional group capable of reacting with the reactive group of (A) and a polymerizable compound (B) having an ethylenic double bond in a molecule described below. It is preferable that there is a difference. Therefore, as a binder compound (A) having a reactive group or a crosslinking agent (D) having a functional group capable of reacting with the reactive group of the binder compound (A) having the reactive group, at least a siloxane bond or carbon The compound having a monofluorine bond forms a low refractive index binder matrix when a compound having a refractive index of about 1.5 is used as the polymerizable compound (B) having an ethylenic double bond. Is preferred for

Such a binder compound having a reactive group may be used alone or in combination of two or more. Usually, it is 10% by mass or more and 95% by mass in the holographic recording composition. /. Or less, and more than 20% by mass and 80% by mass. /. The following is preferable.

In addition, the crosslinking agent (D) having a functional group capable of reacting with the reactive group of the binder compound (A) having a reactive group, which is an essential component of the holographic recording composition, includes a reactive group of the binder compound. There is no particular limitation as long as the binder compound has a hydroxyl group.For example, if the binder compound has a hydroxyl group, a crosslinking agent having a isocyanate group, a carbodiimide group or a metal alkoxide has an isocyanate group if it has a mercapto group, When the crosslinker having a carboximide group or an epoxy group has a carboxyl group, the crosslinker has an oxetane group, a carpoimideimide group, an oxazine group or a metal alkoxide, and when the crosslinker has an amino group, an isocyanate group or an epoxy group Alternatively, a crosslinking agent having an acid anhydride, etc. has an epoxy group If the crosslinking agent has a mercapto group, an amino group, a carboxyl group or a sulfonic acid group, the crosslinking agent has an oxetane group, and the crosslinking agent has a sulfoxyl group or a sulfonic acid group, and if it has an isocyanate group Is a cross-linking agent having a hydroxyl group, a mercapto group or an amino group, and a hydroxyl group, a mercapto group, a carboxy group or a sulfonic acid group when having a carbodiimide group, and a carboxyl group when having a carbodiimide group. Alternatively, a crosslinking agent having a sulfonic acid group or the like can be used. The crosslinking agent may have a functional group capable of reacting with the binder resin having a reactive group from the beginning, or the functional group may be developed by applying another energy such as heat or light. A cross-linking agent such as a precursor may be used.

These may be used alone or in combination of two or more. Usually, the amount is 0.1% by mass or more and 70% by mass or less in the holographic recording yarn. Is

It is preferable that the content be 0.5% by mass or more and 50% by mass or less. Next, the polymerizable compound (B) having an ethylenic double bond in the molecule, which is an essential component of the holographic recording composition, will be described.

The polymerizable compound having an ethylene double bond in the molecule used in the present invention can be used without particular limitation as long as it is a compound having an ethylenic double bond. When considering adhesion of the polymer and compatibility with the binder compound (化合物), a compound having an acyloxy group or an amylamide group in the molecule is preferable. Further, from the viewpoint of steric hindrance in radical polymerization ( (Meth) Compounds having an atarylyl group are more preferred. The term “(meth) atalyloyl group” in the present invention means an atalyloyl group or a methacryloyl group.

Examples of such a compound having a (meth) atalyloyl group include, as compounds having one (meth) atalyloyl group, (meth) atalylate and (meth) acrylamide of phenol, nonylphenol and 2-ethylhexanol. And (meth) acrylates and (meth) acrylamides of alkylene oxide adducts of these alcohols. Compounds having two (meth) atalyloyl groups include di (meth) atalylates of bisphenol A, isocyanuric acid and fluorene (meth) acrylamide and di (meth) adducts of alkylene oxide adducts of these alcohols. Acrylate (meth) acrylamide, ethylenedaricol dipropylene di (meth) acrylate and (meth) acrylamide of polyanolealkylene glycol such as pyridolinone and the like. Compounds having three (meth) atalyloyl groups include pentaerythritol, trimethylolpropane, tri (meth) atalylate and tri (meth) acrylamide of isocyanuric acid, and alkylene oxide adducts of these alcohols. There are tri (meth) atalylate and tri (meth) acrylamide, etc., and as a compound having four or more (meth) atalyloyl groups Examples include pentaerythritol and dipentaerythritol poly (meth) acrylate and poly (meth) acrylamide. Also, conventionally known acrylic or acrylamide-based monomers and oligomers such as urethane acrylates having a urethane bond as a main chain, polyester acrylates having an ester bond as a main chain, and epoxy (meth) acrylate in which acrylic acid is added to an epoxy compound. In the present invention, these can be appropriately selected and used.

In the compound having a plurality of (meth) atalyloyl groups, (meth) acrylate alone or (meth) acrylamide alone may be used, or (meth) acrylate and (meth) acrylamide may be used alone. May be used.

In addition, the crosslinking agent (D) having a functional group capable of reacting with the reactive group of the binder compound (A) having a reactive group described above is obtained by diffusion polymerization with respect to the strength of the binder matrix formed. In order to make the refractive index difference between the polymer of the polymerizable compound (B) having an ethylenic double bond and the polymer more remarkable, the binder compound (A) and / or the crosslinking agent are used as the refractive index of the polymerizable compound. It is preferable to use one higher or lower than (D). In particular, when a compound having a refractive index of about 1.5 is used as the binder compound (A) and Z or the crosslinking agent (D), it is preferable to use a compound having a refractive index of 1.55 or more as the polymerizable compound (B). It is preferable because a polymer of the polymerizable compound (B) having a high refractive index can be obtained.

The polymerizable compound (B) having an ethylenic double bond in the molecule may be used alone or in combination of two or more. 2% by mass or more and 80% by mass or less, and further 5% by mass. /. As described above, the content is preferably 70% by mass or less.

Furthermore, in the present invention, a binder compound having a reactive group other than the above-mentioned essential components (A) A reaction accelerator for the purpose of accelerating the reaction with the crosslinking agent (D) having a functional group capable of reacting with the reactive group of the binder compound (A), a thermal expansive agent for the purpose of preventing heat shrinkage after recording, Polymerization inhibitor to prevent thermal polymerization during preparation of recording composition, plasticizer or heat-meltable compound to adjust liquid viscosity during preparation of recording composition, etc. You can.

Next, the holographic recording medium of the present invention will be described in detail.

In the holographic recording medium of the present invention, a holographic recording layer is sandwiched between a first base material and a second base material, and the holographic recording layer has a binder compound (A) having a reactive group; A polymerizable compound having an ethylenic double bond (B), a photopolymerization initiator (C), and a crosslinking agent having a functional group capable of reacting with the reactive group of the binder compound (A) having the reactive group. (D), and at least the compound represented by the general formula (1) as the photopolymerization initiator (C). The binder compound having a reactive group (A), the polymerizable compound having an ethylenic double bond in the molecule (B), the photopolymerization initiator (C), the binder compound having the reactive group The compound represented by the general formula (1) contained in the recording layer at least as a crosslinking agent (D) having a functional group capable of reacting with the reactive group of (A) and a photopolymerization initiator (C) is as described above. This is the same as that described in detail for the holographic recording composition.

Next, the first base material and the second base material constituting the recording medium will be described. Here, the first base material referred to here is a base material on the side where the information light and the reference light are incident upon holographic exposure for recording information on the recording medium or reproduction light for reproduction. The second substrate refers to a substrate opposite to the first substrate with the holographic recording layer interposed therebetween. The first base material and the second base material used for the recording medium of the present invention are transparent and do not cause expansion or contraction or bending at the ambient temperature of use, and are inert to the above-described recording composition. Any suitable material can be used without limitation. Examples of such a substrate include quartz glass, soda glass, potash glass, lead crystal glass, borosilicate glass, aluminosilicate glass, titanium crystal glass, and crystallized glass. Various resins such as glass, polycarbonate, polyacetanol, polyarylate, polyetherenoether terketone, polysulfone and polyethersulfone, polyimide such as polyimide-amide and polyetherimide, polyamide, and polyolefin such as cyclic olefin-opening polymer. Can be mentioned.

Among the above-mentioned substrates, information light and reference light are used in view of thickness fluctuation and gas permeability with respect to environmental temperature and humidity during holographic exposure, and light transmittance of light source wavelength used during holographic exposure. It is more preferable that the material of the first substrate on the side where light is incident be glass. As the material of the second base material, glass is preferable as in the first base material. However, if the apparatus provided with the focus correction mechanism is used to read out the holographically recorded information by the CCD, the expansion and contraction rate and the thickness variation may be varied. A substrate made of a resin may be used instead of a substrate such as a glass in which is pressed.

Further, the transmittance of the light incident on the first base material on the side where the information light and the reference light are incident is preferably 70% or more, and more preferably, 80% or more causes a loss of light reaching the holographic recording layer. It is more preferable because it is small. In order to increase the transmittance as described above, it is preferable that an anti-reflection treatment is applied to the first substrate surface opposite to the surface on which the holographic recording layer is laminated. is not particularly limited as lower refractive index than the first substrate as, for example _{_{AIF 3, M g F 2,}} a l F 3 'M g F 2, C a F 2 or the like of inorganic metal fluorides, Fluorine sources such as vinylidene fluoride and Teflon (R) Organic fluorides such as homopolymers, copolymers, graft polymers, block polymers and modified polymers modified with functional groups containing fluorine atoms, etc. Is also preferable because the refractive index becomes low.

The method of providing a layer made of a fluorine-based compound on a substrate cannot be determined unequivocally depending on the type of the support-fluorine-based compound, but a sol-gel method, a vacuum deposition method, a sputtering method, A known method such as a CVD method or a coating method, or a method described in JP-A-7-27902, JP-A-2001-123264, JP-A-2001-264509 or the like can be appropriately selected and used.

Such an antireflection layer cannot be unconditionally defined by the surface treatment or material of the base material, but is usually in the range of 0.001 to 20 im, preferably in the range of 0.005 to 10 im.

Further, for a recording medium such as used in a holographic recording / reproducing apparatus disclosed in Japanese Patent Application Laid-Open No. 2002-123949 and World Patent No. 99/57719, the surface on which the second base material holographic recording layer is laminated or its It is preferable that a reflection layer is provided on the opposite surface. When such a reflection layer is provided, the reflectance is preferably 70% or more with respect to the wavelength of the light to be reflected, and more preferably 80% or more. Is more preferable. Such a reflective layer is not particularly limited in its material as long as a desired reflectance can be obtained, but can usually be laminated by providing a thin film of a metal or the like on the surface of the base material. For example, in order to form such a reflective layer, it can be provided as a metal thin film, a metal single crystal or a polycrystal by a known method such as a vacuum evaporation method, an ion plating method, and a sputtering method. The metals used for such treatment include aluminum, zinc, antimony, indium, selenium, tin, tantalum, chromium, lead, gold, silver, platinum, nickel, niobium, germanium, silicon, molybdenum, manganese, and tungsten. Metals such as ten and palladium can be formed by one kind or a combination of two or more kinds. The thickness of the metal thin film layer cannot be specified unconditionally depending on the surface properties and material of the base material, but is usually in the range of 1 to 3000 nm, preferably in the range of 5 to 2000 nm.

On the other hand, in the case of holographic recording media, a recording medium having a high storage capacity can be manufactured by making the holographic recording layer as thick as possible. In consideration of the above, in the present invention, when the thickness of the first base material is dl, the thickness of the second base material is d2, and the thickness of the holographic recording layer is Dh, 0.15≤Dh / It is preferable that the relationship (d 1 + d 2) ≤ 2.0 be satisfied.

Here, at 0.15> Dh / (d1 + d2), the thickness of the holographic recording layer cannot be increased, or even if the recording layer is increased, the thickness of the base material increases, and the overall recording medium The thickness becomes thick. In this case, the mass of the recording medium alone increases, which may result in a load on the drive system of the apparatus, which is not preferable. When Dh / (d 1 + d 2)> 2.0, the thickness of the recording medium can be reduced while maintaining the thickness of the recording layer. The thickness of the recording layer increases, the recording medium surface accuracy and the thickness of the recording layer vary with the operating temperature, and the thickness of the recording layer fluctuates when unexpected stress is applied. Is not preferable because there is a case where the position is shifted.

Further, from the viewpoint of energy loss during holographic exposure, it is preferable that the relationship between the thickness d1 of the first base material and the thickness d2 of the second base material is d1≤d2. In order to ensure the thickness, it is more preferable that the ratio of the thickness of d 1 and d 2 is in the range of 0. SO ^ d 1 Zd 2 ≤1.00. Also, the thickness D h of the holographic recording layer cannot be determined unconditionally due to the diffraction efficiency, dynamic range, spatial resolution, etc. of the recording layer, but it is usually preferably not less than 200 ^ u ni and not more than 2.0 mm. If it is less than 200 μm, a recording medium with a high storage capacity cannot be obtained, and if it is thicker than 2.0 mm, unevenness in the surface accuracy of the recording medium and the thickness of the recording layer at the operating temperature will occur. Unfavorable because there are cases.

On the other hand, the shape of the recording medium is not particularly limited as long as it is suitable for a holographic recording / reproducing apparatus. For example, US Pat. No. 5,719,691 and JP-A-2002-1 If it is used for the device described in 23949, etc., a disk-shaped device is preferable, and if the device described in World Patent No. 9/57771 9 is used, Card-shaped ones are preferred.

As described above in detail, a method for producing a recording medium includes mixing the holographic recording layer forming composition by mixing the holographic recording composition by heating at room temperature or, if necessary, under safelight. After being prepared and degassed to suppress polymerization inhibition during holographic exposure, the holographic recording layer-forming composition at room temperature or heated as needed is applied to the first substrate, A recording medium can be manufactured by laminating the two substrates so that air bubbles do not enter so as to have a predetermined recording layer thickness, and finally sealing the end. In addition, the first base material and the second base material are fixed to a mold under a safe light so as to have a predetermined gap, and the room temperature or, if necessary, the heated hodallagraphic recording composition is filled with air bubbles. Fill the space between the first base material and the second base material by injection molding so that there is no air, or suction under reduced pressure so that air bubbles do not enter, and finally seal the edges to produce the recording media can do. The term “under safelight” as used herein refers to the wavelength and wavelength of light at which the photopolymerization initiator is activated. When using light when forming an inner matrix, it refers to the work with the wavelength of light used cut.

When a recording medium is produced by bonding, the holographic recording layer forming composition may be applied on the second substrate instead of the first substrate as described above. It may be applied to both the first and second substrates. Further, when sealing the end portions of the first base material, the holographic recording layer, and the second base material, a liquid sealing material that can be sealed may be cross-linked and sealed. The sealing may be performed in advance using a sealing material on a ring having a predetermined thickness.

Next, a method for recording information on a holographic recording medium will be described in detail. In a first embodiment of the holographic recording method of the present invention, a holographic recording layer is sandwiched between a first base material and a second base material, and the holographic recording layer has a reactive group. It can react with the binder compound (A), the polymerizable compound (B) having an ethylenic double bond in the molecule, the photopolymerization initiator (C), and the reactive group of the binder compound (A) having the reactive group. A method for performing holographic recording on a mouth opening recording medium comprising a crosslinking agent having a functional group (D), and comprising at least a compound represented by the general formula (1) as the photopolymerization initiator (C), Before the holographic exposure, the binder compound (A) having a reactive group and the crosslinking agent (D) having a functional group are crosslinked by heat or light irradiation that does not activate the photopolymerization initiator (C). Recorded The holographic exposure based on the information is performed to activate the photopolymerization initiator (C), and the active species diffuse-polymerizes the polymerizable compound (B) having an ethylenic double bond in the molecule. It is characterized by recording information on holographic recording media.

Generally, when a thick film layer is applied, a recording layer forming composition without a solvent for dilution In the case of a solid or high-viscosity composition, it is difficult to obtain a uniform film thickness or to remove bubbles trapped during the preparation of the composition. Therefore, when the recording layer forming composition is prepared, fluidity is required at room temperature or in a heated state. In particular, when the recording layer forming composition is liquid at room temperature and has low viscosity, it is difficult to secure flatness as a recording medium, or the polymerizable compound (B) after recording information by holographic exposure. It is not preferable because the polymer formed by the diffusion polymerization may be displaced in the recording layer.

Therefore, before the holographic exposure, the binder compound (A) having a reactive group and the crosslinking agent (D) having a functional group are applied to the holographic recording medium containing the above essential components by heat or light. Cross-linking by light irradiation that does not activate the polymerization initiator (C) ensures a flatness by forming a binder matrix, and a recording layer of a polymer formed by diffusion polymerization of the polymerizable compound (B). It can be prevented from moving inside.

After the pine matrix has been formed, holographic exposure based on the information to be recorded is performed to activate the photopolymerization initiator (C). Information can be recorded on the holographic recording medium by diffusing and polymerizing the polymerizable compound (B) having a heavy bond.

The crosslinking reaction for forming the binder matrix in the present recording method may be carried out by reacting all of the binder compound (A) having a reactive group and the crosslinking agent (D) having a functional group. May be caused to react only partially within a range that does not occur. Furthermore, after the information has been recorded on the holographic recording medium, a binder having a reactive group remaining by light and, if necessary, heat is applied for the purpose of fixing the recorded holographic information. Compound (A) and a crosslinking agent having a functional group (D), Further, it is preferable to polymerize the polymerizable compound (B) having an ethylenic double bond in the molecule. In this case, it is preferable that the light used for the exposure be collectively exposed to the entire recording medium.

According to a second aspect of the holographic recording method of the present invention, a holographic recording layer is sandwiched between a first base material and a second base material, and the holographic recording layer has a reactive group. A functional group capable of reacting with the reactive groups of the compound (A), the polymerizable compound (B) having an ethylenic double bond in the molecule, the photopolymerization initiator (C), and the binder compound (A) having the reactive group In a method for performing holographic recording on a holographic recording medium comprising a crosslinking agent (D) having a group and at least a compound represented by the general formula (1) as the photopolymerization initiator (C), information to be recorded Holographic exposure to activate the photopolymerization initiator (C), and diffusion polymerization of the polymerizable compound (B) having an ethylenic double bond in the molecule by this active species. After recording information on the holographic recording media, stabilize the recorded information by applying heat or light to the entire holographic recording media after the information recording on the holographic recording media is completed. Features.

This embodiment is different from the first embodiment described above in that, when the recording layer forming composition is prepared, a composition that is fluid in a heated state but does not flow at room temperature, or at room temperature unless shear stress is applied. This is an effective recording method for a holographic recording medium in which a recording layer is formed by a recording layer forming composition having a thixotropic property such as gelation. In such a recording medium, there is no practical problem with respect to securing the flatness of the recording medium and preventing movement of the polymer formed by diffusion polymerization of the polymerizable compound (B). The power that can be used to record information on holographic recording media After completion, the remaining binder compound (A) having a reactive group and the crosslinking agent (C) having a functional group are irradiated with light and heat applied as necessary for the purpose of fixing the recorded holographic information. It is preferable to polymerize D), and the polymerizable compound (B) having an ethylenic double bond in the molecule. In this case, it is preferable that the light used for the exposure be exposed all at once to the entire recording medium.

The method and apparatus for recording / reproducing the holographic recording medium of the present invention may be timely used as long as they can record and reproduce on the recording medium of the present invention among various proposed ones. Examples of such a recording / reproducing method and apparatus include, for example, U.S. Patent Nos. 5,719,691, 5,838,467, 6,163,391, 6,414,296 and U.S. Pat. 2002-136143, JP-A-9-305978, JP-A-10-124872, JP-A-11-21 9540, JP-A-2000-98862, JP-A-2000-298837, JP-A-2001-23619, JP-A-2002-83431 No. 2002-123949, No. 2002-123948, No. 2003-43904, World Patent No. 99/57719, No. 02/05270, No. 02/75727 and the like. As the laser used in the recording and reproducing method and apparatus as described above, the light source is a laser capable of activating a photopolymerization initiator in a recording medium and capable of opening a hole, and capable of reading a recorded hologram. Any light source can be used without particular limitation. Examples of such a light source include a semiconductor laser in the blue region, an argon laser, a He—Cd laser, a frequency doubled YAG laser, a He—Ne laser, a Kr laser, A semiconductor laser in the near infrared region can be used.

Example

Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not limited to the example.

<< Preparation of holographic recording layer forming composition >>

(Holographic recording layer forming composition 1)

9 8. A solution was prepared 1 containing 8 6 mass ^_0/0 4 one click Rolf enyl Atari rate (refractive index 1.5 3 6)及Pi 1.1 4% by weight of di-heptyl tin dilaurate. Then, under safelight, 1.70 g of solution 1, 25.19 g of diisocyanate-terminated polypropylene glycol (molecular weight = 247 1), and aω-dihydroxypolypropylene glycol (molecular weight =: 425) 4 70 g were mixed and separately prepared 5 · 10 g of 4-chlorophenylacrylate (described above) and 0.03 g of a photoinitiator [Circa Special Chemical Co., Ltd., Irgacure 784] and 0 Initiator solution 1 containing 0.0063 g of sensitizing dye (Dye-1) was added to the above solution. After the composition prepared at the end was deaerated with nitrogen, the gas components contained therein were removed with an ultrasonic cleaner to prepare a holographic recording layer forming composition 1 for comparison.

Dye— 1

(Holographic recording layer forming composition 2)

9.697 g of polypropylene glycol diglycidyl ether (Kyoeisha Chemical Co., Ltd., Epolite 200 P), 6.042 g of pentaerythritol (tetrakismercaptopropionate) and 0.840 g of 2, Solution 2 was prepared by mixing 4,6-tris (dimethylaminomethyl) phenol. Prepared separately 2. 1 94 g of 4-promostyrene (refractive index: 1.594), 0.126 g of a photopolymerization initiator [Irgacure 784, manufactured by Chino Special Chemical Co., Ltd.] and 0.0126 g of a color sensitive element (Dy e-1 ) Was added to solution 2 described above. After the composition prepared at the end was deaerated with nitrogen, the gas components contained therein were removed by an ultrasonic cleaner to prepare a holographic recording layer forming composition 2 for comparison.

(Holographic recording layer forming composition 3)

9. 697 g of polypropylene glycol, 'Recall Diglycidyl Ether (Kyoeisha Chemical Co., Ltd., Epolite 200P)', 6.02 g of pentaerythritol (tetrakismercaptopropionate) and 0.840 g of 2,4, Solution 2 was prepared by mixing 6-tris (dimethylaminomethyl) phenol. Separately prepared 2.189 g of 4-chlorophenoleacrylate (refractive index: 1.536) and 0.126 g of photopolymerization initiator [Circa Special Chemical Co., Ltd., Irgacure 784] and 0.0126 g Initiator solution 3 containing sensitizing dye (Dye-1: supra) was added to solution 2 described above. Finally, the prepared yarn was deaerated with nitrogen, and the contained gas components were removed with an ultrasonic cleaner to prepare a comparative holographic recording layer forming composition 3.

(Holographic recording layer forming composition 4-14)

The formation of the holographic recording layer was performed except that the photopolymerization initiator (C) shown in Table 1 was used instead of the photopolymerization initiator and the photosensitive dye used in the preparation of the holographic recording layer forming composition 1 described above. Holographic recording layer forming compositions 4 to 14 were prepared in the same manner as in composition 1.

(Holographic recording layer forming composition 15-: L 9)

The photopolymerization initiator and the photopolymerization initiator used in the preparation of the holographic recording layer forming composition 2 described above. The holographic recording layer-forming composition was prepared in the same manner as in the formation of the holographic recording layer 2 except that the photopolymerization initiator (C) shown in Table 1 was used instead of the sensitizing dye. 15-19 were prepared. Photopolymerization initiator (C)

Type Addition amount [g]

Holographic recording layer forming composition 4 C-1 0.074 Holographic recording layer forming composition 5 C-1 0.110 Holographic recording layer forming composition 6 C—2 0.071 Holographic recording layer forming composition 7 C-1 0.083 Holographic Recording layer forming composition 8 C-1 4 0.092 Holographic recording layer forming composition 9 C—5 0.080 Holographic recording layer forming composition 10 C-1 8 0.091 Holographic recording layer forming composition 11 C—9 0.097 Holographic recording layer Forming composition 12 C-1 10 0.096 Holographic recording layer forming composition 13 C-1 11 0.090 Holographic recording layer forming composition 14 C-12 0.087 Holographic recording layer forming composition 15 C-1 0.147 Holographic recording layer forming composition Material 16 C—2 0.141 Holographic recording layer forming composition 17 C—6 0.169 Holographic recording layer forming composition 18 C-1 7 0.203 Holographic recording Layer forming composition 19 C one 12 0.173

C-1

C-2

C-3

C-4

C-1 5

-B— C ₄ H ₉ (n)

6-0

2-0

.-0

9-0 εε 89 £ 00 / 00Ζάΐ / 13ά 980 980 contract OAV C— 10

C-1 11

C-12

(Holodaratic recording layer forming composition 20-27)

9.976 g of epoxypropoxypropyl-terminated polydimethylsiloxane (Silaplane FM-5511, manufactured by Chisso Corporation), 2.953 g of pentaerythritol (tetrakismercaptopropionate) and 0.411 g of Solution 4 was prepared by mixing 2,4,6-tris (dimethylaminomethyl) phenol. Next, to this solution 4, the compound (B) having a (meth) acryloyl group shown in Table 2 and the photopolymerization initiator (C) were added, and the mixture was stirred and dissolved to form a uniform solution. Finally, remove the homogeneous solution with nitrogen. After applying air, the contained gas components were removed by an ultrasonic cleaner to prepare holographic recording layer forming compositions 20 to 27.

Table 2

B-1: 4—Chrono phenol acrylate

B-2: Bisphenol A E0-modified diatalylate [Alonitas M210, manufactured by Toagosei Co., Ltd.]

B-3: Paracumyl phenoxyethylene glycol methacrylate [Shin Nakamura Chemical Co., Ltd., ester CMP-1E] B— 4: Paracumyl phenoxyethylene glycol acrylate [Shin Nakamura Chemical Co., Ltd., K ester A— CMP— 1E] B-5: Hydroxethylation o-Phenylphenol acrylate [M-ester A—L4, manufactured by Shin-Nakamura Chemical Co., Ltd.] B-6: Hydroxethylation naphthol acrylate [Shin-Nakamura Chemical B-7: 9,9-bis (3-pheninolee 4-acryloniole polyoxyethoxy) fluorene

(Holographic recording layer forming composition 28-38)

The binder compound (A) having a reactive group shown in Table 3 and 2.413 g of a hydroxylated compound] 3-naphthol acrylate [manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-NP-1 E] and 10. 201 g of a photopolymerization initiator was added and dissolved by stirring to obtain a uniform solution 4. To this, a crosslinking agent (D) having a functional group capable of reacting with the reactive group of the binder compound (A) having the reactive group described in Table 3 and a crosslinking accelerator (E) were added and stirred to form a uniform solution. Thereafter, deairing was performed with nitrogen, and finally, the airborne components contained therein were removed with an ultrasonic cleaner to prepare holographic recording layer forming compositions 28 to 38.

Table 3

<< Production of holographic recording media >>

Translation method 1)

As the first and second substrates, antireflection treatment was performed on one side of 0.5 mm thick glass so that the reflectance of incident light perpendicular to the wavelength of 52 nm was 0.1%. . A transparent polyethylene terephthalate sheet having a thickness shown in Table 4 was used as a spacer on the surface of the first base material which had not been subjected to the antireflection treatment, and the holographic recording layer forming composition shown in Table 4 was used as the first material. Attached to the base material, the surface of the second base material which has not been subjected to the anti-reflection treatment is pasted on the holographic recording layer forming composition so that the air layer is not involved, and the first base material is put through a spacer. And the second substrate. Finally, the end was sealed with a moisture-curable adhesive and left at room temperature for 24 hours to produce a holographic recording medium.

(Preparation method 2)

In the same manner as in Production Method 1, the ends were sealed with a moisture-curable adhesive, and then left at 45 ° C for 24 hours to produce the mouth-drainage recording media described in Tables 4 and 5. .

(Preparation method 3)

The first base material is reduced in thickness by subjecting one surface of the glass having a thickness of 0.5 mm to an anti-reflection treatment so that the reflectance by incident light perpendicular to the wavelength of 532 nm is 0.1%. One side of a glass of 5 mm was subjected to aluminum vapor deposition so that the reflectance with incident light perpendicular to the wavelength of 532 nm was 90% to produce second base materials. Next, a transparent polyethylene terephthalate sheet having a thickness shown in Table 6 was used as a spacer on the surface of the first base material which had not been subjected to the antireflection treatment, and the holographic recording layer forming composition described in Table 6 was used as a spacer. Attaching to one base material, then bonding the aluminum-deposited surface of the second base material onto the holographic recording layer forming composition so that the air layer does not get caught in the spacer. And the first base material and the second base material were bonded together. Finally, the end was sealed with a moisture-curable adhesive, and left at room temperature for 24 hours to produce a holographic recording medium.

(Preparation method 4)

In the same manner as in Production Method 3, the ends were sealed with a moisture-curable adhesive, and then left at 45 ° C. for 24 hours to produce the holographic recording media shown in Table 6.

Table 4

Holographic holographic

Production method J ^ Recording media No. Recording layer forming composition No.

Recording medium 1 Composition 2 Preparation method 1 0.20 Recording medium 2 Composition 2 Preparation method 1 Recording medium 3 Composition 3 Preparation method 1 0.20 Recording medium 4 Composition 4 Preparation method 1 0.20 Recording medium 5 Composition 5 Preparation method 1 0.20 Recording Media 6 Composition 5 Preparation method 1 0.50 Recording medium 7 Composition 11 Preparation method 1 Recording medium 8 Composition 13 Preparation method 1 0.20 Recording medium 9 Composition 14 Preparation method 1 0.20 Recording medium 10 Composition 15 Preparation method 1 0.20 Recording medium 11 Composition 15 Preparation method 1 Recording medium 12 Composition 16 Preparation method 1 0.20 Recording medium 13 Composition 17 Preparation method 1 0.20 Recording medium 14 Composition 18 Preparation method 1 0.20 Recording medium 15 Composition 19 Preparation method 1 0.20 ο 7 "16 Composition O Recording media 20 Preparation method 1 oo 0.20

M C

Recording medium 17 Composition 21 Preparation method 1 0.2 o o0 ooo Recording medium 18 Composition 21 Preparation method 1 Recording medium 19 Composition 22 Preparation method 1 0.20 Recording medium 20 Composition 23 Preparation method 1 0.20 Recording medium 21 Composition 24 Preparation method 1 0.20 Recording medium 22 Composition 29 Preparation method 1 0.20 Recording medium 23 Composition 29 Preparation method 1 0.50 Composition 1 Preparation method 2 0.20 Recording medium 25 Composition 1 Preparation method 2 Recording medium 26 Composition 3 Preparation method 2 0.20 Recording medium 27 Composition 4 Preparation method 2 0.20 Recording medium 28 Composition 5 Preparation method 2 0.20 Recording medium 29 Composition 5 Preparation method 2 0.50 Recording medium 30 Composition 6 Preparation method 2 Recording medium 31 Composition 7 Preparation method 2 0.20 3684

42

Table 5

Holographic holographic

Manufacturing method Storage (mm) Recording media No. Recording layer formed and composition No.

Recording medium 32 Composition 8 Preparation method 2 0.20 Recording medium 33 Authentic material 9 Preparation method 2 0.20 Recording medium 34 Composition 10 Preparation method 2 0.20 Recording medium 35 Composition 11 Preparation method 2 0.20 Recording medium 36 Composition 12 Preparation method 2 0.20 Recording medium 37 Composition 13 Preparation method 2 0.20 Recording medium 38 Composition 14 Preparation method 2 0.20 Recording medium 39 Composition 20 Preparation method 2 0.20 Recording medium 40 Composition 21 Preparation method 2 0.20 Recording medium 41 Composition 21 Preparation method 2 0.50 Recording medium 42 Composition 25 Preparation method 2 0.20 Recording medium 43 Composition 26 Preparation method 2 0.20 Recording medium 44 Composition 27 Preparation method 2 0.20 Recording medium 45 Composition 27 Preparation method 2 0.50 Recording medium 46 Composition 29 Preparation method 2 0.20 Recording medium 47 Composition 29 Preparation method 2 0.50 Recording medium 48 Composition 32 Preparation method 2 0.20 Recording medium 49 Composition 33 Preparation method 2 0.20 Recording medium A 50 composition 34 preparation method 2 0.20 recording medium 51 composition 35 preparation method 2 0.20 recording medium 52 composition 36 preparation method 2 0.20 recording medium 53 composition 36 preparation method 2 0.50 recording medium 54 composition 37 preparation method 2 0.20 recording Medi T55 Composition 38 Preparation Method 2 0.20

Table 6

Holographic Holographic Manufacturing Method Thickness Recording Media No. Recording Layer Forming Composition N. (mm) Recording medium 56 Composition 2 Preparation method 3 0.20 Recording medium 57 Composition 2 Preparation method 3 0.50 Recording medium 58 Composition 3 Preparation method 3 0.20 Recording medium 59 Composition 3 Preparation method 3 0.50 Recording medium 60 Composition 15 Preparation method 3 0.20 Recording medium 61 Composition 16 Preparation method 3 0.20 Recording medium 62 Composition 17 Preparation method 3 0.20 Recording medium 63 Composition 18 Preparation method 3 0.20 Recording medium 64 Composition 19 Preparation method 3 0.20 Recording medium 65 Composition 20 Preparation method 3 0.20 Recording medium 66 Composition 21 Preparation method 3 0.20 Recording medium 67 Composition 22 Preparation method 3 0.20 Recording medium 68 Composition 23 Preparation method 3 0.20 Recording medium 69 Composition 24 Preparation method 3 0.20 Recording medium 70 Composition 25 Manufacturing method 3 0.20 Recording media 71 Composition 27 Manufacturing method 3 0.20

B Recorder 72 Composition 27 Preparation method 3 0.50 Recording medium 73 Composition 29 Preparation method 3 0.20 Recording medium 74 Composition 1 Preparation method 4 0.20 Recording medium 75 Composition 1 Preparation method 4 0.20 Recording medium 76 Composition 3 Preparation method 4 0.20 Recording media 77 Composition 3 Preparation method 4 0.20 Recording media 78 Composition 8 Preparation method 4 0.20 Recording media 79 Composition 2. Preparation method 4 0.20 Recording medium 80 Composition 20 Preparation method 4 0.50 Recording medium 81 Composition 22 Preparation method 4 0.20 Recording medium 82 Composition 23 Preparation method 4 0.20 Recording medium 83 Composition 25 Preparation method 4 0.20 Recording medium 84 Composition 27 Preparation method 4 0.20 Recording medium 85 Composition 27 Preparation method 4 0.50 Recording medium 86 Composition 28 Preparation method 4 0.20 Recording medium 87 Composition 30 Preparation method 4 0.20 Recording medium 88 Composition 31 Preparation method 4 0.20 Recording medium 89 Composition 34 Preparation method 4 0.20 Recording medium 90 Composition 35 Preparation method 4 0.20 Recording medium 91 Composition 36 Preparation method 4 0.20 Recording medium composition 36 Preparation method 4 0.50 Recording medium 93 Composition 37 Preparation method 4 0.20 Recording medium 94 Composition 38 Preparation Method 4 0.20 《Recording and evaluation on holographic recording media》

(Recording and evaluation on the Eguchi Dalafic Recording Media 1)

The holographic recording medium produced as described above is written with a series of multiplexed holograms according to the procedure described in US Pat. No. 5,719,691, and the sensitivity (recording energy) and refractive index are recorded according to the following method. The contrast was measured and evaluated, and the obtained results are shown in Tables 7 and 8.

(Sensitivity measurement)

A digital pattern is displayed on a holographic recording medium under a safe light using a holographic manufacturing device equipped with an Nd: YAG laser (532 nm), and this digital image is displayed with an energy of 0.1 to 5 Om J / cm ^2. A hologram was obtained by patterning holographic exposure. Next, using a Nd: YAG laser (532 nm) as reference light, the generated reproduction light was read by a CCD, and the minimum exposure amount at which a good digital pattern was reproduced was measured as sensitivity (S).

(Evaluation of contrast of refractive index)

The refractive index contrast was determined from the diffraction efficiency measured according to the following method. The diffraction efficiency was measured using an ART25C type spectrophotometer manufactured by JASCO Corporation. A photomanoremeter with a slit of 3 mm in width was used to measure the circumference of a sample with a radius of 20 cm. Installed above. Monochromatic light with a width of 0.3 mm was incident on the sample at an angle of 45 degrees, and diffracted light from the sample was detected. The ratio of the largest value other than the specularly reflected light to the value when directly incident light was received without placing a sample was defined as the diffraction efficiency, and the refractive index contrast (Δη) was determined from the diffraction efficiency of the obtained hologram. Table 7

Holographic Δη Self-recording medium No. (X10 ³ ) Comparative example 1-1 Recording medium 1 20 1.7 Comparative example 11 2 Recording medium 2 30 2.5 Comparative example 11 3 Recording medium 3 18 2.2 Present invention 1-1 Recording medium 4 1.5 3.8 The present invention 1-2 Recording media 5 1.3 3.7 The present invention 1-3 Recording media 6 1.5 4.5 The present invention 1-4 Recording media 7 1.3 3.7 The present invention 1-5 The recording media 8 1.5 3.9 The present invention 1-6 The recording media 9 2.5 4.2 Invention 1-7 Recording media 10 1.1 4.1 Invention 1-8 Recording media 11 1.4 4.9 Invention 1-9 Recording media 12 1.2 Ο 4.2 Invention 11 10 Recording media 13 1.2 4.2 Transliteration 1_11 Recording media 14 1.1 4.3 Present invention 11 12 Recording medium 15 1.6 4.2 Comparative example 11 4 Recording medium 24 15 2.3 Comparative example 11 5 Recording medium 25 20 2.6 Comparative example 11 6 Recording medium 26 20 2.5 Present invention 1-13 Recording medium 27 1.7 4.1 Recording medium of the present invention 11-14 Recording medium 29 1.7 4.7 present invention 1 one 16 recording medium 30 1.5 4.3 present invention 1- 17 recording medium 31 1.6 4.4 present invention 1 18 recorded Meda 32 1.5 4.2 present invention 1 one 19 recording medium 33 1.5 4.4

Table 8

It can be seen that the recording medium of the present invention has higher sensitivity and higher contrast than the comparative example.

(Recording and evaluation on holographic recording media 2)

The holographic recording medium produced as described above was written with a series of multiplexed holograms according to the procedure described in US Pat. No. 5,711,691, and the sensitivity (recording energy), The contrast of the refractive index was measured and evaluated, and the obtained results are shown in Table 9.

(Sensitivity measurement) The holographic recording medium under safelight, Nd: at holographic manufacturing apparatus provided with a YAG laser (5 32 nm) to display the digital pattern, with the energy of 0. 1~5 Om J / cm ^2, the digital A hologram was obtained by patterning holographic exposure. Next, the holographic recording media was processed for 5 minutes under a sunshine feed meter of 70,000 no lettuce, and the processed recording media was used as a reference light using a Nd: YAG laser (532 nm) under safelight. The generated reproduction light was read by a CCD, and the minimum exposure amount at which a good digital holographic pattern was reproduced was measured as sensitivity (S).

Table 9

Holographic Δη recording Meda No. (X10 one ³⁾ Comparative Example 2-1 recording medium 1 25 1.9 Comparative Example 2-2 recording medium 2 35 2.8 Comparative Example 2-3 recording medium 3 20 2.5 invention 2-1 recording medium 4 1.6 4.1 The present invention 2-2 Recording medium 5 1.3 3.9 The present invention 2-3 Recording medium 61, 4, 4 The present invention 2-4 The recording medium 7 1.4 3.9 The present invention 2-5 The recording medium 8 1.5 4.0 The present invention 2 6 Recording media 9 2.6 4.3 Invention 2-7 Recording media 10 1.3 4.3 Invention 2-8 Recording media 11 1.6 5.2 Invention 2-9 Recording media 12 1.o3 4.4 Invention 2-10 Recording media 13 1.2 4.3 Invention 2—11 Recording media 14 1.2 4.5 Invention 2—12 Recording media 15 1.6 4.4 Invention 2—13 Recording media 16 1.2 5.2 Invention 2—14 Recording media 17 1.5 5.2 Invention 2—15 Recording media 18 2.6 6.5 Invention 2-16 Recording media 19 1.5 6.9 Present invention 2-17 Recording media 20 1.4 7.2 Present invention 2-18 Recording media 21 1.6 7.4 Present invention 2-19 Recording media 22 1.9 7.4 Present invention 2-20 Recording media 23 2.6 8.9 Present invention 2-21 Recording media 42 1.8 7.5 Present invention 2-22 Recording media 43 2.8 7.8 Invention 2-23 Recording media 44 1.5 8.2 Invention 2-24 Recording media 45 2.6 9.3 Invention 2-25 Recording media 50 1.2 8.6 Invention 2 26 Recording media 51 1.3 8.7 Invention 2 27 Recording media 52 1.3 8.8 Invention 2—28 Recording media 53 1.9 9.6 Invention 2—29 Recording media 54 1.2 9.1 Invention 2—30 Recording media 55 1.3 8.9 It can be seen that the recording medium of this effort has high sensitivity and high contrast as compared with the comparative example.

(Recording and evaluation on holographic recording media 3)

The holographic recording medium produced as described above is disclosed in

A series of multiplexed holograms was written according to the procedure described in No. 23,949, and the sensitivity (recording energy) was measured and evaluated according to the following method. The results obtained are shown in Table 10.

(Sensitivity measurement)

Holographic storage media under safe light, Nd: YAG laser (5

3 in holographic manufacturing apparatus having a 2 nm) to display the digital pattern, 0. 1 at 5 0 m J / cm ² of Enenoregi one, to obtain a hologram by holographic worship exposed the digitalized patterned Was. Next, the holographic recording media was processed under a 70,000 lux sunshine feedmeter for 5 minutes, and the processed recording media was used as a reference light with a Nd: YAG laser (532 contract) under safelight. The generated reproduction light was read using a CCD, and the minimum exposure at which a good digital pattern was reproduced was measured as the sensitivity (S).

Table 10

Holographic recording media No. S [mj / cm ² ] Comparative example 3-1 Recording medium 56 18 Comparative example 3-2 Recording medium 57 25 Comparative example 3-3 Recording medium 58 15 Comparative example 3-4 Recording medium 59 20 Invention 3-1 Recording media 60 1 Invention 3-2 Recording media 61 1.1 Invention 3-3 Recording media 62 1.1 Invention 3-4 Recording media 63 1.1 Invention 3-5 Recording media 64 1.5 Invention 3-6 Recording Media 65 1 Invention 3-7 Recording media 66 1.2 Invention 3-8 Recording media 67 1.3 Invention 3-9 Recording media 68 1.2 Invention 3-10 Recording media 69 1.3 Invention 3-11 Recording media 70 1.4 Invention 3—12 Recording medium 71 1.4 Present invention 3—13 Recording medium 72 1.9 Invention 3—14 Recording medium 73 1.5 Comparative example 3—5 Recording medium 74 12 Comparative example 3—6 Recording medium 75 15 Comparative example 3—7 Recording medium 76 18 Comparative example 3—8 Recording media 77 25 Invention 3-15 Recording media 78 1.3 Invention 3-16 Recording media 79 1 Invention 3_17 Recording media 80 1.5 Invention 3-18 Recording media 81 1.6 Invention 3-19 Recording media 82 1.5 Invention 3-20 Recording media 83 1.6 Invention 3-21 Recording medium 84 1.3 Invention 3-22 Recording medium 85 2.2 Invention 3-23 Recording medium 86 1.4 Invention 3-24 Recording medium 87 1.5 Invention 3-25 Recording medium 88 1.5 Invention 3 26 Recording media 89 1.1 Invention 3—27 Recording media 90 1.2 Invention 3—28 Recording media 91 1.1 Invention 3—29 Recording media 92 1.4 Invention 3—30 Recording media 93 1 Invention 3—31 Recording media 94 1.3 It is clear that the recording medium of the present invention has higher sensitivity than the comparative example. 【The invention's effect】

According to the present invention, a holographic recording medium having high sensitivity and high contrast and a holographic recording method using the same can be provided.

Claims

The scope of the claims

1. A holographic recording layer is sandwiched between a first base material and a second base material, and the holographic recording layer has a binder compound (A) having a reactive group; Crosslinking agent having a functional group capable of reacting with the reactive group of the polymerizable compound (B) having a heavy bond, the photopolymerization initiator (C), and the binder compound (A) having the reactive group

(D) and at least a compound represented by the following general formula (1) as the photopolymerization initiator (C):

General formula (1)

(Wherein, Dy e + represents a cationic dye, Ι ^ ~Ι ₄ each represent a substituted or unsubstituted alkyl group, Ariru group, Ararukiru group, an alkenyl group, an alkynyl group, a heterocyclic group, or Shiano group, also Two or more of Ri to R ₄ may combine with each other to form a ring.)

2. At least one location substituent represented by 1 ^ to 1 ₄ in the general formula photopolymerization initiator represented by (I) (C) is a substituted or unsubstituted alkyl group, Ararukiru group, Aruke nil 2. The holographic recording medium according to claim 1, wherein the holographic recording medium is a alkynyl group or a substituted or unsubstituted aryl group or a heterocyclic group.

3. Click of Dye ⁺ of the photopolymerization initiator (C) represented by the general formula (1) On dyes are methine dyes, polymethine dyes, triary methane dyes, indolin dyes, azine dyes, thiazine dyes, xanthene dyes, oxazine dyes, ataridin dyes, cyanine dyes, posocyanin dyes, hemicyanine dyes, rhodocyanin dyes, azamethine 2. The holographic recording medium according to claim 1, wherein the holographic recording medium is a dye, a stylinole dye, a pyrylium dye, a thiopyrylium dye, or a coordination metal complex represented by the following general formula (2).

General formula (2) M ^{n +} (L) _χ

(Where Μ represents a metal atom, η represents an integer of 1 to 4, L represents a ligand, and X represents an integer of 1 to 6)

4. The method according to claim 3, wherein L, which is a ligand of the coordination metal complex represented by the general formula (2), is a dye capable of chelating at least two sites with respect to the metal. The holographic recording media described in section.

5. A crosslinking agent (D) having a functional group capable of reacting with a reactive group of the binder compound (Α) having the reactive group or the binder compound (Α) having the reactive group contains siloxane in the molecule. 2. The holographic recording medium according to claim 1, wherein the holographic recording medium is a compound having a bond or a carbon-fluorine bond.

6. The reactive group of the binder compound (Α) having a reactive group is a hydroxyl group, a mercapto group, a carboxyl group, an amino group, an epoxy group, an oxetane group, an isocyanate group, a carbodiimide group, an oxazine group and a metal alkoxide. Claim 1 characterized in that it is at least one type of reactive group selected from the group consisting of: Holographic recording media.

7. The holographic recording medium according to claim 5, wherein the binder compound having a reactive group (A) is liquid at room temperature or has a melting point of 50 ° C. or less.

8. The polymerizable compound having an ethylenic double bond in the molecule (B) force The polymerizable compound having a (meth) acryloyl group in the molecule is contained therein. Holographic record described in

9. The holographic composition according to claim 1, wherein the polymerizable compound (B) having an ethylenic double bond in the molecule contains at least a compound having a refractive index of 1.55 or more. Recording media.

10.When the thickness of the first base material is d1, the thickness of the second base material is d2, and the thickness of the holographic recording layer is Dh, 0.15≤Dh / (d1 + d2 2. The holographic recording medium according to claim 1, wherein a relationship of ≤ 2.0 is satisfied.

11. The holographic recording medium according to claim 10, wherein the thickness Dh of the holographic recording layer is 200 / zm or more and 2.0 mm or less.

1 2. The holographic device according to claim 10, wherein the relationship between the thickness d1 of the first base material and the thickness d2 of the second base material is d1 d2. Recording media.

13. The method according to claim 1, wherein the first base material is transparent, and a surface opposite to a surface on which the holographic recording layer is laminated is subjected to an anti-reflection treatment. Holographic recording media.

14. The holographic recording medium according to claim 1, wherein the material of the first base material is glass.

15. A reflection layer having a reflectance of 70% or more is laminated on the surface of the second base material on which the holographic recording layer is laminated or on the opposite surface thereof. Holographic recording media according to item 1.

16. The holographic recording medium according to claim 1, wherein the holographic recording medium has a disk shape.

1 7. The holographic recording medium according to claim 1, wherein the shape is a card shape.

18. A holographic recording layer is sandwiched between the first base material and the second base material, and the holographic recording layer comprises a binder compound (A) having a reactive group, A polymerizable compound (B) having an ethylenic double bond, a photopolymerization initiator (C), and a crosslinking agent (D) having a functional group capable of reacting with the reactive group of the binder compound (A) having the reactive group. And holographic recording on a holographic recording medium containing at least the compound represented by the general formula (1) as the photopolymerization initiator (C). After crosslinking the binder compound (A) having a functional group with the crosslinking agent (D) having a functional group by heat or light irradiation that does not activate the photopolymerization initiator (C), the hologram based on the information to be recorded is obtained. Graphic exposure is performed to activate the photopolymerization initiator (C), and to polymerize the polymerizable compound (B) having an ethylenic double bond in the molecule with this active species by diffusion polymerization. Holographic recording how, characterized in that recording information on A.

19. After the information recording on the holographic recording medium is completed, the recorded information is stabilized by further irradiating the entire holographic recording medium with heat or light. The holographic recording method described in item 18 of the scope.

20. A holographic recording layer is sandwiched between the first base material and the second base material, and the holographic recording layer comprises a binder compound (A) having a reactive group, A polymerizable compound (B) having a heavy bond, a photopolymerization initiator (C) and a crosslinking agent (D) having a functional group capable of reacting with the reactive group of the binder compound (A) having the reactive group. And a holographic recording medium containing at least a compound represented by the general formula (1) as the photopolymerization initiator (C). In the recording method, holographic exposure based on the information to be recorded is performed to activate the photopolymerization initiator (C), and the polymerizable compound having an ethylenic double bond in the molecule (B The information is recorded on the holographic recording medium by diffusing and polymerizing the holographic recording medium. A holographic recording method characterized by stabilizing collected information.